Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/18—Pretreatment of the material to be coated
  • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
  • C23C18/22—Roughening, e.g. by etching
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/1601—Process or apparatus
  • C23C18/1633—Process of electroless plating
  • C23C18/1646—Characteristics of the product obtained
  • C23C18/165—Multilayered product
  • C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/18—Pretreatment of the material to be coated
  • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
  • C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
  • C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
  • C23C18/2073—Multistep pretreatment
  • C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/18—Pretreatment of the material to be coated
  • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
  • C23C18/22—Roughening, e.g. by etching
  • C23C18/24—Roughening, e.g. by etching using acid aqueous solutions
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/18—Pretreatment of the material to be coated
  • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
  • C23C18/28—Sensitising or activating

Definitions

• the present invention relates to a pretreatment process for electroless plating of a resin molded article, comprising an etching treatment step using an etching solution containing a manganate salt; a plating process of a resin molded article comprising an etching treatment step using an etching solution containing a manganate salt; and a treatment agent used in the plating process.
• Resin molded articles have been used as automobile components in recent years to reduce the weight of automobiles. Resins such as ABS resins, PC/ABS resins, PPE resins, and polyamide resins have been used to achieve this object, and such resin molded articles are often plated with copper, nickel, or the like to provide high quality impressions and a beautiful appearance.
• a common method for forming an electroplating film on a resin molded article comprises degreasing and etching the molded article, optionally followed by neutralization and pre-dipping, and then applying an electroless plating catalyst using a colloidal solution containing a tin compound and a palladium compound, optionally followed by activation (treatment with an accelerator), to perform electroless plating and electroplating sequentially.
• a chromic acid mixture which is a mixed solution of chromium trioxide and sulfuric acid
• chromic acid mixtures which contain toxic hexavalent chromium, adversely affect work environments.
• safe disposal of the liquid waste requires reduction of the hexavalent chromium to a trivalent chromium ion, and then neutralization and precipitation, thus requiring complicated treatment for the disposal of the liquid waste. Therefore, in consideration of workplace safety and adverse effects of the liquid waste on the environment, avoiding the use of chromic acid-containing etching solution is preferable
• Etching solutions that contain a manganate salt as an active ingredient are known as alternatives to chromic acid mixtures.
• an alkaline etching solution containing a permanganate salt and alkali metal hydroxide see Non-patent Document 1 below
• an acidic etching solution containing a permanganate salt and inorganic acid see Non-patent Document 2 below
• inferior deposition of the electroless plating sometimes occurs during electroless plating that is performed after catalyst application, and further, a manganese component carried into a catalyst application solution adversely affects the deposition performance of the electroless plating. Accordingly, to allow the formation of a good electroless plating film in the case that etching treatment is performed using a manganate salt-containing etching solution, improvements in the treatment process are desired.
• a primary object of the present invention is to provide a novel electroless plating process for a resin molded article, particularly, a process that is capable of forming a plating film with sufficient adhesion in the case that an etching treatment is performed using a manganate salt-containing etching solution in an electroless plating treatment of a resin molded article; and a treatment agent that is usable in the treatment process.
• the present inventors conducted extensive research to achieve the above object. As a result, they found the following. When a resin molded article is etched using an etching solution containing a manganate salt as an active ingredient, and then subjected to a post-treatment using a treatment agent containing a reducing compound and an inorganic acid, manganate salts that are attached to the surface of the resin molded article during etching can be almost completely removed, which prevents a manganese component from entering into a catalyst solution, and ensures the formation of a good electroless plating film. The inventors further found that, when a surface-conditioning treatment using an amine compound is performed after the post-treatment, the amount of the adsorbed catalyst is increased, which allows stable production of a good plating film.
• the inventors found the following. In applying a catalyst on a substrate to be plated (i.e., catalyzing the substrate) with an acidic mixed colloidal solution containing palladium chloride and stannous chloride, activation is conducted after catalyst application, using a treatment agent that contains carboxylic acids, carboxylic acid salts, phosphorus compounds, carbonic acids, or a boric acid as active ingredients, which prevents deposition of electroless plating on the surface of a jig holding the resin molded article to be treated, enabling the formation of an electroless plating film only on the surface of the target resin molded article. Electroless plating and electroplating can be therefore performed sequentially without changing the jig, which simplifies the plating process. Based on the above findings, the present inventors conducted further research. The present invention was thus accomplished.
• the present invention relates to the following treatment process after etching of a resin molded article, plating process of a resin molded article, and treatment agent used in the processes.
• Item 1 A pretreatment process for electroless plating of a resin molded article, the pretreatment process comprising etching the resin molded article using an etching solution containing a manganate salt, and then bringing the resin molded article into contact with an aqueous solution containing a reducing compound and an inorganic acid.
• Item 2 The pretreatment process according to Item 1, wherein the etching solution containing a manganate salt is an aqueous solution containing 20 to 1,200 g/L of an inorganic acid, 0.01 to 40 g/L of a manganate salt, and 1 to 200 g/L of at least one member selected from the group consisting of halogen oxoacids, halogen oxoacid salts, persulfate salts, and bismuthate salts.
• the etching solution containing a manganate salt is an aqueous solution containing 20 to 1,200 g/L of an inorganic acid, 0.01 to 40 g/L of a manganate salt, and 1 to 200 g/L of at least one member selected from the group consisting of halogen oxoacids, halogen oxoacid salts, persulfate salts, and bismuthate salts.
• Item 3 A post-treatment agent of a resin molded article etched with an etching solution containing a manganate salt, the agent comprising an aqueous solution containing a reducing compound and an inorganic acid.
• Item 4 A process for plating a resin molded article comprising the steps of:
• Item 5 The process according to Item 4, wherein the aqueous solution containing an amine compound used in step (3) above comprises at least one member selected from the group consisting of ethyleneamines represented by the formula: H 2 N(CH 2 CH 2 NH) n H, wherein n is an integer of 1 to 5, polyethyleneimines, and propylamines represented by the formula: wherein R 1 is a propyl group or an aminopropyl group optionally having a substituent on nitrogen atom, and R 2 is a propyl group, an aminopropyl group optionally having a substituent on nitrogen atom, or a hydrogen atom.
• ethyleneamines represented by the formula: H 2 N(CH 2 CH 2 NH) n H, wherein n is an integer of 1 to 5, polyethyleneimines, and propylamines represented by the formula: wherein R 1 is a propyl group or an aminopropyl group optionally having a substituent on nitrogen atom, and R 2 is a propyl group, an amino
• Item 6 The process according to Item 4 or 5, wherein the process for applying an electroless plating catalyst in step (4) above comprises bringing the resin molded article into contact with a mixed colloidal solution containing 0.01 to 0.6 g/L of palladium chloride, 1 to 50 g/L of stannous chloride, and 100 to 400 ml/L of 35% hydrochloric acid, and then bringing the article into contact with an aqueous solution containing at least one member selected from the group consisting of carboxylic acids, carboxylic acid salts, phosphorus compounds, carbonic acid salts, and a boric acid.
• Item 7 A process for plating a resin molded article comprising performing electroless plating by the process according to any one of Items 4 to 6, and then performing electroplating.
• Item 8 The plating process according to any one of Items 4 to 7, wherein the manganate salt-containing etching solution is an aqueous solution containing 20 to 1,200 g/L of an inorganic acid, 0.01 to 40 g/L of a manganate salt, and 1 to 200 g/L of at least one member selected from the group consisting of halogen oxoacids, halogen oxoacid salts, persulfate salts, and bismuthate salts.
• the manganate salt-containing etching solution is an aqueous solution containing 20 to 1,200 g/L of an inorganic acid, 0.01 to 40 g/L of a manganate salt, and 1 to 200 g/L of at least one member selected from the group consisting of halogen oxoacids, halogen oxoacid salts, persulfate salts, and bismuthate salts.
• a surface conditioning agent for use in a process for plating a resin molded article comprising an etching treatment step using a manganate salt-containing etching solution, the agent comprising an aqueous solution containing an amine compound.
• An activating agent for use in a catalyst application step of a process for plating a resin molded article comprising an etching treatment step using a manganate salt-containing etching solution, the agent comprising an aqueous solution containing at least one member selected from the group consisting of carboxylic acids, carboxylic acid salts, phosphorus compounds, carbonic acid salts, and a boric acid.
• a substrate to be treated is a resin molded article.
• the kind of the resin is not particularly limited.
• a particularly good electroless plating film can be formed on various resin materials that have heretofore been etched using a chromic acid-sulfuric acid mixture.
• a good electroless plating film can be formed on styrene-based resins such as acrylonitrile-butadiene-styrene copolymer resins (ABS resins); resins having an acrylic rubber component (AAS resins) in place of the butadiene rubber component of ABS resin; resins having an ethylenepropylene rubber component (AES resins) in place of the butadiene rubber component of ABS resin; acrylonitrile-styrene copolymer resins (AS); polystyrene resins (PS); and the like.
• ABS resins acrylonitrile-butadiene-styrene copolymer resins
• AS acrylonitrile-styrene copolymer resins
• PS polystyrene resins
• Alloy resins of styrene-based resins as mentioned above and polycarbonate (PC) resins are also preferable. It is also possible to use polyacrylonitrile resins (PAN), polycarbonate resins (PC), polyamido resins (PA), as well as Noryl, polyphenylene ether resins, polyphenylene oxide resins, and like resins that have excellent heat resistance and physical properties.
• PC polycarbonate
• PA polyamido resins
• a good plating film with excellent appearance and physical properties can be formed even on a large article having a large surface area.
• large resin products include automobile parts and accessories such as radiator grills, hubcaps, medium or small emblems, and door handles; exterior equipment used in the electrical or electronic field; faucet fittings used in places where water is supplied; game machine-related products such as pachinko components; and the like.
• etching is conducted using an etching solution containing a manganate salt as an active ingredient.
• etching solutions containing a manganate salt as an active ingredient include alkaline etching solutions containing a permanganate salt and alkali metal hydroxide as active ingredients, acidic etching solutions containing a permanganate salt and an inorganic acid as active ingredients, and the like. All of such known etching solutions can be used in the present invention.
• alkaline etching solution examples include, but are not limited to, an aqueous solution containing about 40 to about 70 g/L of permanganate salts such as potassium permanganate and sodium permanganate, and about 10 to about 30 g/L of sodium hydroxide.
• permanganate salts such as potassium permanganate and sodium permanganate
• the acidic etching solution include, but are not limited to, an aqueous solution containing about 0.1 to about 50 g/L of permanganate salts such as potassium permanganate and sodium permanganate, and about 100 to about 600 g/L of inorganic acids, such as sulfuric acid, phosphoric acid, hydrochloric acid, and nitric acid.
• permanganate salts such as potassium permanganate and sodium permanganate
• inorganic acids such as sulfuric acid, phosphoric acid, hydrochloric acid, and nitric acid.
• Etching treatment using such etching solutions may be according to a known method.
• etching solution comprising an aqueous solution containing about 20 to about 1,200 g/L of an inorganic acid, about 0.01 to about 40 g/L of a manganate salt, and about 1 to about 200 g/L of at least one member selected from the group consisting of halogen oxoacids, halogen oxoacid salts, persulfate salts, and bismuthate salts.
• a good electroless plating film with high adhesion can be formed on a resin molded article by a process comprising etching the resin molded article using the etching solution described above, then applying an electroless plating catalyst, and subsequently performing electroless plating.
• examples of inorganic acids include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, boric acid, carbonic acid, sulfurous acid, nitrous acid, phosphorous acid, borous acid, hydrogen peroxide, perchloric acid, and the like. Of these, sulfuric acid and hydrochloric acid are particularly preferable. Such inorganic acids can be used singly or in a combination of two or more.
• the content of the inorganic acid is about 20 to about 1,200 g/L, and preferably about 300 to about 1,000 g/L.
• the manganate salts are permanganate salts.
• Permanganate salts are not particularly limited, as long as they are water-soluble salts. Examples of permanganate salts include sodium permanganate, potassium permanganate, and the like. Such manganate salts can be used singly or in a combination of two or more.
• the content of the manganate salts is about 0.01 to about 40 g/L, and preferably about 0.1 to about 10 g/L.
• halogen oxoacids include hypohalous acid, halous acid, halogen acid, perhalogen acid, and the like.
• halogen oxoacid salts include water-soluble salts of the above-mentioned halogen oxoacids, such as sodium salts of halogen oxoacids, and potassium salts of halogen oxoacids.
• persulfate salts include water-soluble persulfate salts such as sodium persulfate, potassium persulfate, ammonium persulfate, and the like.
• bismuthate salts include water-soluble bismuthate salts such as sodium bismuthate, potassium bismuthate, and the like.
• Halogen oxoacids, halogen oxoacid salts, persulfate salts, and bismuthate salts can be used singly or in a combination of two or more.
• at least one member selected from the group consisting of perhalogen acids such as perchloric acid, perbromic acid, and periodic acid, salts of these perhalogen acids, persulfate salts, and bismuthate salts is preferably used.
• the etching solution should contain at least one member selected from the group consisting of halogen oxoacids, halogen oxoacid salts, persulfate salts, and bismuthate salts in an amount of about 1 to about 200 g/L, and preferably about 10 to about 100 g/L.
• the etching solutions include aqueous solutions containing: at least one inorganic acid selected from the group consisting of sulfuric acid and hydrochloric acid; at least one manganate salt selected from the permanganate salts; and at least one halogen oxoacid compound selected from the group consisting of perchloric acid, perbromic acid, periodic acid, and salts thereof.
• the surface of the resin molded article, which is used as a substrate to be treated is brought into contact with the etching solution.
• the method therefor is not particularly limited, as long as the method is capable of bringing the surface of the article into sufficient contact with the etching solution.
• a method of spraying the etching solution over the article may be used.
• efficient treatment can be achieved by immersion of the article into the etching solution.
• the etching conditions are not particularly limited, and can be suitably selected according to the desired degree of etching.
• the temperature of the etching solution may be about 30°C to about 70°C, and the immersion time may be about 3 to about 30 minutes.
• the surface of the resin molded article, which is used as a substrate to be treated is extremely dirty, the surface may be degreased according to a usual method, prior to etching.
• a post-treatment is carried out using an aqueous solution (sometimes referred to as a "post-treatment agent") containing a reducing compound and an inorganic acid.
• aqueous solution sometimes referred to as a "post-treatment agent”
• This treatment allows efficient removal of manganese attached to the resin surface, thereby preventing manganese from entering into a catalyst solution, and improving the deposition performance of the electroless plating. As a result, a good electroless plating film with excellent uniformity can be formed.
• etching when etching is performed using an etching solution comprising an aqueous solution containing inorganic acids, manganate salts, and at least one member selected from the group consisting of halogen oxoacids, halogen oxoacid salts, persulfate salts, and bismuthate salts, not only manganese but halogen compounds attached to the resin surface can be removed in an almost complete manner by performing a post-treatment using a post-treatment agent that contains a reducing compound and inorganic acid.
• the etching solution fully exhibits its excellent properties to thereby form a good electroless plating film with excellent uniformity and high adhesion.
• Examples of reducing compounds contained in the post-treatment agent include polyvalent metal compounds having a reducing activity such as tin chloride, tin sulfate, iron chloride, and iron sulfate; saccharides such as glucose, mannitol, sucrose, fructose, maltose, and lactose; boron compounds such as sodium borohydride and dimethylamine borane; aldehyde compounds such as formaldehyde, acetaldehyde, propionaldehyde, acrolein, benzaldehyde, cinnamaldehyde, and perillaldehyde; ascorbic acids such as ascorbic acid, ascoryl stearate, sodium ascorbate, L-ascorbyl palmitate, and L-ascorbic-acid A glucoside; hydrazines such as hydrazine, hydrazine sulfate, hydrazine hydrochloride, hydrazin
• Such reducing compounds can be used singly or in a combination of two or more.
• tin chloride, tin sulfate, ascorbic acid, sodium ascorbate, hydrazine sulfate, hydrazine hydrochloride, hydroxylamine sulfate, hydroxylamine hydrochloride, and thiosulfuric acid are preferable.
• inorganic acids examples include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, carbonic acid, nitrous acid, phosphorous acid, borous acid, hydrogen peroxide, perchloric acid, nitrogen peroxide, and the like.
• Such inorganic acids can be used singly or in a combination of two or more. Particularly, sulfuric acid and hydrochloric acid are preferable.
• the concentration of the reducing compound in the post-treatment agent is preferably about 0.5 to about 100 g/L, and more preferably about 5 to about 30 g/L.
• the concentration of the inorganic acid is preferably about 5 to about 500 g/L, and more preferably about 30 to about 100 g/L.
• the treatment method using a post-treatment agent is not particularly limited, as long as the method is capable of bringing the article into sufficient contact with the post-treatment agent.
• efficient treatment can be achieved by immersion of the article into the post-treatment agent.
• the article may be immersed in a post-treatment agent having a temperature of about 20 to about 60°C for about 1 to about 10 minutes.
• the surface of the article can be treated using an aqueous solution (hereinafter referred to as a "conditioning agent") containing an amine compound.
• a conditioning agent aqueous solution
• This treatment can increase the adsorption amount of the catalyst on the surface of the article used as a substrate to be treated, enabling the stable formation of a good plating film.
• a catalyst-accelerator method i.e., a method comprising performing a catalyzing treatment using an acidic mixed colloidal solution (catalyst solution) containing palladium chloride and stannous chloride, and then performing an activation treatment
• the adsorption amount of the catalyst can be increased by conditioning the surface with the aforementioned conditioning agent even when the concentration of palladium in the catalyst solution is low.
• this improves the deposition performance of the electroless plating, and the subsequent electroplating enables the formation of a plating film with a good appearance.
• the amine compound contained in the conditioning agent may be at least one compound selected from the group consisting of ethyleneamines represented by formula: H 2 N(CH 2 CH 2 NH) n H 2 , wherein n is an integer of 1 to 5, polyethyleneimines, and propylamines represented by the following formula:
• R 1 is a propyl group or an aminopropyl group optionally having a substituent(s) on nitrogen atom
• R 2 is a propyl group, an aminopropyl group optionally having sunstituent(s) on nitrogen atom, or a hydrogen atom.
• the propyl group may be either an n-propyl group or an isopropyl group.
• the aminopropyl group optionally having a substituent(s) on nitrogen atom, examples of the substituents include lower alkyl groups such as methyl groups etc.
• ethyleneamines include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc.
• Polyethyleneimine which is a water-soluble polymer obtained by polymerizing ethyleneimines, preferably has a number average molecular weight of about 300 to about 70,000, and more preferably about 600 to about 10,000.
• propylamines examples include propylamine, isopropylamine, diisopropylamine, diaminopropylamine, methylaminopropylamine, dimethylaminopropylamine, etc.
• particularly preferable amine compounds are propylamine, isopropylamine, diaminopropylamine, etc. These amine compounds can be used singly or in a combination of two or more.
• the content of the amine compound is preferably about 0.01 to about 50 g/L, and more preferably about 0.02 to about 10 g/L.
• the surface conditioning method using the conditioning agent is not particularly limited. After performing post-etching treatment and washing with water, the resin molded article may be brought into contact with the conditioning agent. In general, efficient treatment can be achieved by immersion of the article into the conditioning agent.
• the treatment conditions are not particularly limited, but, for example, the article may be immersed in a conditioning agent of about 10 to about 40°C, for about 0.5 to about 5 minutes.
• the pH of the conditioning agent is not particularly limited. However, when the resin molded article is formed of two types of resins that include a portion on which a plating film should not be deposited, or when the resin molded article include a non-plating portion on which a plating resist film is formed, selective deposition of the plating film only on a target resin surface is required.
• the pH is preferably about 12 or less, and more preferably about 8 or less; the lower limit of the pH is preferably about 4. Within such a pH range, the plating film can be formed with high selectivity.
• a buffer may be added to suppress the change in pH caused by the introduction of the etching solution into the conditioning agent.
• buffers include carbonic acid, boric acid, phosphoric acid, phosphorous acid, oxalic acid, acetic acid, malonic acid, malic acid, citric acid, glycolic acid, gluconic acid, succinic acid, glycine, nitrilodiacetic acid, nitrilotriacetic acid, 2-aminoethanol, diethanolamine, triethanolamine, and salts thereof, etc.
• Such buffers can be used singly or in a combination of two or more.
• the content of the buffer is not particularly limited. In general, it is preferably about 1 to about 50 g/L.
• a catalyst for electroless plating is applied.
• the process for applying an electroless plating catalyst is not particularly limited.
• An electroless plating catalyst such as palladium, silver, ruthenium, or the like may be applied according to a known method.
• known processes of applying a palladium catalyst include the so-called catalyst-accelerator method, sensitizing-activating method, alkali catalyst method, and the like.
• the catalyst-accelerator method is particularly preferable since the plating film is likely to be deposited on the resin molded article in a uniform manner.
• a commonly used acidic mixed colloidal solution containing palladium chloride and stannous chloride is usable.
• an acidic mixed colloidal solution containing about 0.01 to about 0.6 g/L of palladium chloride, about 1 to about 50 g/L of stannous chloride, and about 100 to about 400 ml/L of 35% hydrochloric acid can be used.
• a treatment method using the catalyst solution involves immersion of the resin molded article in the catalyst solution of about 20 to about 40°C, for about 1 to about 10 minutes.
• activation may be conducted using an aqueous sulfuric acid solution, aqueous hydrochloric acid solution, aqueous alkali-metal hydroxide solution, and like accelerator solutions, according to a usual method.
• Specific treatment processes and conditions of the aforementioned method are according to known methods.
• the process comprising catalyzing a substrate to be treated using a catalyst solution comprising a mixed colloidal solution containing about 0.01 to about 0.6 g/L of palladium chloride, about 1 to about 50 g/L of stannous chloride, and about 100 to about 400 ml/L of 35% hydrochloric acid, and then activating the substrate using an aqueous solution (hereinafter sometimes referred to as "activating agent") containing at least one member selected from the group consisting of carboxylic acids, carboxylic acid salts, phosphorus compounds, carbonic acid salts, and a boric acid, the catalyst component attached on the surface of the jig coated by a flexible vinyl chloride sol can be almost completely removed, which prevents the deposition of the electroless plating on the surface of the jig. As a result, electroless plating and electroplating can be performed sequentially without changing the jig, largely simplifying the process.
• activating agent aqueous solution
• carboxylic acids contained in the activating agent include monocarboxylic acids, such as formic acid, acetic acid, propionic acid, methylacetic acid, butyric acid, ethylacetic acid, n-valeric acid, n-butanecarboxylic acid, acrylic acid, propiolic acid, methacrylic acid, palmitic acid, stearic acid, oleic acid, linolic acid, and linolenic acid; dicarboxylic acids, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, lepargilic acid, sebacic acid, maleic acid, and fumaric acid; aliphatic hydroxy acids, such as glycolic acid, lactic acid, tartronic acid, glyceric acid, malic acid, tartaric acid, citramalic acid, citric acid, isocitric acid, leucine
• Salts of such carboxylic acids are not particularly limited, as long as they are water-soluble salts. Examples thereof include sodium salts, potassium salts, and like alkali metal salts, ammounium salts, etc.
• Examples of phosphorus compounds include trisodium phosphate, potassium phosphide, potassium pyrophosphate, sodium pyrophosphate, etc.
• Examples of carbonic acid salts include ammonium carbonate, potassium carbonate, potassium hydrogen carbonate, calcium carbonate, sodium hydrogen carbonate, sodium carbonate, barium carbonate, etc.
• the concentration of at least one member selected from the group consisting of carboxylic acids, carboxylic acid salts, phosphorus compounds, carbonic acid salts, and a boric acid is preferably about 1 to about 100 g/L, and more preferably about 5 to about 50 g/L.
• the substrate may be immersed in the activating agent of about 30 to about 50°C for about 1 to about 7 minutes.
• pre-dipping Prior to application of a catalyst, pre-dipping can be performed using an aqueous hydrochloric acid solution, according to a usual method. Thereby, it is possible to prevent a pretreatment agent from entering into a catalyst application solution.
• Pre-dipping may be performed by immersing the substrate in an aqueous solution containing about 20 to about 300 ml/L of 35% hydrochloric acid at a temperature of about 15 to about 30°C, for about 0.5 to about 3 minutes.
• an aqueous solution containing about 20 to about 300 ml/L of 35% hydrochloric acid at a temperature of about 15 to about 30°C, for about 0.5 to about 3 minutes.
• the conditions are not limited thereto.
• a highly uniform electroless plating film having a good adhesion can be formed on the surface of the resin molded article by performing the electroless plating after applying the catalyst according to the above-mentioned method.
• the electroless plating solution may be any known autocatalytic electroless plating solution.
• electroless plating solutions include electroless nickel plating solutions, electroless copper plating solutions, electroless cobalt plating solutions, electroless nickel-cobalt alloy plating solutions, electroless gold plating solutions, and the like.
• the electroless plating conditions may be according to known methods. If necessary, two or more layers of electroless plating film may be formed.
• electroplating may be further performed.
• activation may be optionally performed using an aqueous solution of an acid, alkali or the like, and then electroplating is performed.
• the kind of electroplating solution is not particularly limited.
• the electroplating solution can be suitably selected from known electroplating solutions according to the purpose.
• a highly uniform plating film with an extremely high adhesion can be formed on a resin molded article.
• the plating process that comprises etching a resin molded article using a manganate salt-containing etching solution, and then treating the resin molded article using the post-treatment agent of the present invention, the following remarkable effects can be achieved.
• Treatment procedure Kind of treatment agent Treatment condition Component Content Temperature time Alkaline 50 g/L degreasing solution ("ACE CLEAN A-220"; Degreasing produced by 40°C 3 Okuno Chemical min. Industries Co., Ltd.) ⁇ Potassium permanganate 0.5 g/L Etching Sodium perchlorate 5 g/L 65°C 10 98% Sulfuric acid 250 ml/L min. ⁇ Post-treatment Post-treatment agent in Tables 2 and 3 50°C 5 min. ⁇ Conditioning Ethylenediamine 5 g/L 25°C 1 min.
• Post-treatment agent of the present invention 1 2 3 4 5 6 7 8 9 10 Reducing Compound Glucose (g/L) 20 Hydrazine (g/L) 20 Ascorbic acid (g/L) 20 Citric acid (g/L) 20 Sodium borohydride (g/L) 20 Tin chloride (g/L) 20 Formaldehyde (g/L) 20 Hydroxylamine hydrochloride (g/L) 20 Sodium thiosulfate (g/L) 20 Potassium iodide (g/L) 20 Hydrochloric acid (g/L) 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100
• electroless nickel plating was performed according to the procedure as shown in Table 1.
• the percentage of the electroless plating film formed on the resin molded article was measured to evaluate the deposition performance of electroless plating.
• the amounts of manganese and halogen adsorbed on the surface of the resin molded article were measured according to the ICP emission spectrochemical analysis. The results are shown in Table 4 below.
• Table 6 Conditioning Agent 1 2 3 4 5 6 7 8 Ethylenediamine (g/L) 5 Diethylene triamine (g/L) 5 Triethylene tetramine 5 Tetraethylene pentamine 5 Pentaethylenehexamine 5 Polyethyleneimine (molecular weight: 600) (g/L) 5 Polyethyleneimine (molecular weight: 1,200) (g/L) 5 Propylamine (g/L) 5
• electroless copper plating and copper electroplating were performed according to the procedure as shown in Table 5.
• the percentage of the electroplating film formed on the surface of the resin molded article was measured to evaluate the deposition performance of the electroplating.
• the amount of Pd adsorbed on the resin surface was measured according to the ICP emission spectrochemical analysis. Additionally, the surface resistance value (k ⁇ ) of the resin surface obtained after electroless copper plating was measured. The results are shown in Table 7 below.
• Table 7 Deposition condition of the copper sulfate electroplating film Adsorption amount of Pd on the resin surface after catalyst application(mg/dm 2 ) Resistance value of the resin surface after electroless copper plating (k ⁇ ) Conditioning agent 1 Full deposition 0.2944 7.85 2 Full deposition 0.2875 8.45 3 Full deposition 0.2815 7.98 4 Full deposition 0.3179 5.31 5 Full deposition 0.3543 4.45 6 Full deposition 0.3871 4.81 7 Full deposition 0.4263 3.85 8 Full deposition 0.3831 4.43 Without conditioning No deposition 0.1188 Unmeasurable due to exceedingly high value
• the treatment according to an immersion method was conducted following the procedure as shown in Table 8 below, to thereby perform electroless plating and electroplating. Treatment agents shown in Table 9 below were used as activating agents. Washing was conducted between each step.
• CRP selector produced by Okuno Chemical Industries Co., Ltd.
• CRP selector produced by Okuno Chemical Industries Co., Ltd.
• CRP Copper MU 5 ml/L 1.5 produced by Okuno A/dm 2 Chemical Industries Co., Ltd.
• CRP Copper A 0.5 ml/L produced by Okuno Chemical Industries Co., Ltd.
• the electroplating deposition on the jig coated by a flexible vinyl chloride sol can be prevented without deteriorating the deposition performance of the plating on the surface of the resin to be plated, by applying a Pd catalyst with a catalyst application solution comprising an acidic mixed colloidal solution of palladium chloride and stannous chloride, and then activating with any one of activating agents 1 to 7.

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